Multi-block sputtering target and associated methods and articles

ABSTRACT

A sputtering target that includes at least two consolidated blocks, each block including an alloy including molybdenum in an amount greater than about 30 percent by weight and at least one additional alloying ingredient; and a joint between the at least two consolidated blocks, the joint being free of any microstructure due to an added bonding agent (e.g., powder, foil or otherwise), and being essentially free of any visible joint line the target that is greater than about 200 μm width (e.g., less than about 50 μm width). A process for making the target includes hot isostatically pressing, below a temperature of 1080° C., consolidated perform blocks that may be surface prepared (e.g., roughened to a predetermined roughness value) prior to pressing.

CLAIM OF BENEFIT OF FILING DATE

This application is a continuation of U.S. patent application Ser. No.15/890,463, filed Feb. 7, 2018, which is a continuation of U.S. patentapplication Ser. No. 15/067,358, filed Mar. 11, 2016, which is adivision of U.S. patent application Ser. No. 13/467,323, filed May 9,2012, which claims the benefit of and priority to U.S. ProvisionalPatent Application No. 61/484,450, filed May 10, 2011, the entiredisclosure of each of which is hereby incorporated herein by reference.

FIELD OF THE INVENTION

The present invention relates generally to sputtering, and moreparticularly to improved multi-component sputtering targets and theirmanufacture and use to produce thin films.

BACKGROUND OF THE INVENTION

Sputtering processes are employed to deposit thin films onto substratesto manufacture any of a variety of devices. Sputtering processestypically involve bombarding a solid sputtering target with energizedparticles to eject atoms from the target. In recent years, there hasbeen a growing need for large area sputtering targets. This isespecially so for certain applications in which large sized products aremade. For example, flat panel displays often require the deposition ofuniform thin films onto a substrate. The demand for larger displays,such as for televisions, continues to strain materials producers todevelop alternative approaches to the efficient supply of suchmaterials.

In one specific application, according to U.S. Pat. No. 7,336,324 (Kimet al), the deposition of a molybdenum-titanium barrier layer onto asubstrate has been employed for the manufacture of a liquid crystaldisplay device. Such application intensifies the need for large displaydevices capable of delivering such materials, particularly targets thatcontain both molybdenum and titanium.

In the manufacture of large area sputtering targets it is often deemedcritical and imperative that the target exhibit uniformity incomposition, microstructure, or a combination of both. For some devicemanufacturers that rely upon the targets to manufacture devices, theslightest imperfections are perceived as a potential quality controlrisk. By way of example, one concern for manufacturers is the potentialformation of particles (e.g., atomic clusters or aggregates having anatomic composition different than the atomic composition of otherregions of the film) during device manufacture. U.S. Pat. No. 6,755,948(Fukuyo et al) discusses the potential effects of particles in thecontext of titanium targets.

Activities in the sputtering target field are illustrated by referenceto a number of patent filings. By way of illustration, U.S. PatentApplication No. 20070089984 describes the formation of a large areasputtering target by the use of a powder between cold-isostaticallypressed blocks of a mixture of molybdenum and titanium powders. The useof such powder generally results in the formation of a conspicuous jointline between adjoining blocks that may appear as a band. Even if suchjoint line does not actually adversely affect performance, itsconspicuous nature is a potential concern for device manufacturers. Forinstance, some manufacturers have the perception that the joint line maycontribute to the formation of undesired particles during sputtering; ifgenerated, there is a belief that such particles potentially mightaffect performance of resulting devices.

U.S. Pat. No. 4,594,219 (Hostatter et al) addresses side-by-sideconsolidation of preforms to form complex or compound shaped articles(e.g., connecting rods and hand wrenches). Consolidation (e.g., by hotisostatic pressing) of molybdenum and/or titanium powder containingperforms is not described. Moreover, particular processing steps toachieve successful results in the consolidation of molybdenum and/ortitanium powder containing performs is also not described.

U.S. Patent Application No. 20050191202 (Iwasaki et al) discloses amolybdenum sputtering target (in which an example is provided of a 70.0at % Mo-30.0 at/% Ti material). The application discloses a requirementfor use of relatively high temperatures and pressures, stating atparagraph 40 that if a pressure below 100 MPa and a temperature below1000° C. is used, “it is hard to produce the sintered body having arelative density of not less than 98%”. The application describes aprocess by which a relatively large size body is consolidated fromsecondary powders and then the sintered body is cut into separatetargets. One example illustrates a further hot plastic working step.

U.S. Patent Application Publication 20050189401 (Butzer) discloses amethod of making a large Mo billet or bar for a sputtering targetwherein two or more bodies comprising Mo are placed adjacent one another(e.g. stacked one on the other) with Mo powder metal present at gaps orjoints between the adjacent bodies. The adjacent bodies are hotisostatically pressed to form a diffusion bond at each of themetal-to-Mo powder layer-to-metal joint between adjacent bodies to forma billet or bar that can be machined or otherwise formed to provide alarge sputtering target. This patent publication appears to disclosebonding of major side surfaces, not edge-to-edge bonding of plates.

U.S. Patent Application No 20080216802 (Zimmerman et al) describesanother method for making large area sputtering targets with amolybdenum-titanium composition, which includes a cold spray depositionstep for joining a plurality of targets at an interface. Thoughacknowledging certain electron beam welding and hot isostatic pressingprocesses to join targets, in paragraphs 185-166 (referring to FIGS. 17and 18), the patent application Indicates that electron beam weldingresults in porosity, and the hot isostatic pressing results in a brittlealloy phase.

U.S. Patent Application No. 20070251820 (Nitta at al) describes anexample of another approach to the manufacture of a molybdenum-titaniumsputtering target. In this publication, diffusion joining (at atemperature of at least 1000° C.) of two or more previously sintered ormelted sputter targets along at least one side. The use of a Mo—Tipowder in the joint is described.

U.S. Patent Application No. 20070289864 (Zhifei et al) identifies a needin large area sputtering targets to fill gaps between multiple targetsections carried on a common backing plate. The patent illustrates thematerial deposition processes between adjoining target portions.Interestingly, the patent recognizes that the manufacture of largemolybdenum plate targets poses difficulties, and the need for efficientmanufacturing.

In view of the above, there remains a need in the art for alternativesputtering targets (especially large size targets, such as targetsexceeding about 0.5 meters, about 1 meter, or even about 2 meters forits largest dimension), and approaches to their manufacture that meetone or any combination of the needs for general uniformity ofcomposition, general uniformity of microstructure, insubstantiallikelihood of particle formation, relatively thin and virtuallyinvisible joint line between target components, or relatively highstrength (e.g., relatively high transverse rupture strength).

SUMMARY OF THE INVENTION

In one aspect, the present teachings meet one or more of the above needsby providing a sputtering target, which may in particular be arelatively large sputtering target (e.g., exceeding about 0.5 meters,about 1 meter, or even about 2 meters for its largest dimension; orstated in another way, exceeding about 0.3 square meters (m²), 0.5 m², 1m², or even 2 m² for the target sputtering surface available forsputtering), comprising a target body that includes at least twoconsolidated blocks, each block including an alloy including molybdenumand at least one additional alloying element: and a joint between the atleast two consolidated blocks, the joint being free of an added bondingagent (e.g., powder, foil or other added material), and beingessentially free of any joint line in a finished target that is visibleto the naked eye (in the absence of magnification), wherein thesputtering target body at the joint exhibits a transverse rupturestrength per ASTM B528-10, of at least about 400 MPa (e.g., at leastabout 690 MPa), throughout the target body (including at the joint). Thetarget body generally throughout may have a Vickers Hardness (HVN) perASTM E384-10 of at least about 260, about 275 or even about 300; forexample, it may have an HVN of about 260 to about 325. The target, thetarget body, the alloy, one or more consolidated blocks, or anycombination thereof may include molybdenum in an amount greater thanabout 30 weight percent. The target, the target body, the alloy, one ormore consolidated blocks, or any combination thereof may includemolybdenum in an amount greater than about 30 atomic percent. Thetarget, the target body, the alloy, the consolidated blocks, or anycombination thereof preferably may include molybdenum in an amountgreater than about 30 volume percent. The target body may have a densityof at least about 0.92, 0.95 or even 0.98 times the theoretical densityof the overall material per ASTM B311-08. For one illustrative targetthat consists essentially of molybdenum and titanium, the target bodymay have a density in the range of about 7.12 to about 7.30, and morespecifically about 7.20 to about 7.25 g/cm³. The sputtering target bodymay also be sufficiently strong so that it withstands, without fracture,routine stresses encountered during subsequent assembly operations(e.g., a three point straightening assembly operation, a creepflattening operation, or some other operation during which the target.

In another aspect, the present teachings meet one or more of the aboveneeds by providing a method for making a sputtering target, comprisingthe steps of: providing first and second blocks (e.g., at least twopartially consolidated preform blocks) each having a prepared (e.g.,roughened or otherwise modified surface, such as at least one edge)surface and each including an alloy including molybdenum in an amountgreater than about 30 percent by weight (wt %), atomic percent (at %) orvolume percent (vol %), and at least one additional alloying element;contacting the prepared surface (e.g., one or more edge surfaces) of thefirst block directly with the prepared surface of the second block inthe substantial absence of any powder (or other intermediate material)between the contacted surfaces to form a contacted joint structure; andisostatically pressing the contacted structure at a temperature that isless than 1100° C. (e.g., less than about 1080° C. or even less thanabout 1000° C.) at a pressure and for a time sufficient to realize aconsolidated joint between the first and second blocks that isessentially free of any joint line width greater than about 300 μm (andmore preferably that is essentially free of any joint line width greaterthan about 300 μm).

In yet another aspect of the teachings herein, it is contemplated thatsputtering is performed using a sputtering target in accordance with thepresent teachings. It also is contemplated that thin films result thatare used in any of a number of electronic devices (e.g., as a barrierlayer, an electrode layer or both), such as one or more of a television,a video display, a smartphone, a tablet computer, a personal digitalassistant, a navigation device, a sensor a portable entertainment device(e.g., video players, music players, etc.), or even a photovoltaicdevice. The thin films may have a reduced amount of structural artifactsattributable to particles as compared with sputtering using targets withpowder joints.

DESCRIPTION OF THE DRAWINGS

FIG. 1a is an illustrative light optical photomicrograph at 25×magnification of a section of a target body formed using a powder joint,with the span of the bracket therein corresponding with the width of thejoint line.

FIG. 1b is an illustrative light optical photomicrograph at 100×magnification of a section of the target body of FIG. 1a formed using apowder joint, with the span of the bracket therein corresponding withthe width of the joint line.

FIG. 2a is an illustrative light optical photomicrograph at 25×depicting a microstructure expected within the present teachings inwhich no bonding agent (e.g., no powder, foil or other added material)is employed for joining between blocks of a target body.

FIG. 2b is an illustrative light optical photomicrograph at 100×depicting a microstructure expected within the present teachings inwhich no bonding agent (e.g. no powder, foil or other added material) isemployed for joining between blocks of a target body.

FIG. 3a is an illustrative light optical photomicrograph at 25×depicting a microstructure expected within the present teachings inwhich no bonding agent (e.g., no powder, foil or other added material)is employed for joining between blocks of a target body, and in whichsurface roughness of blocks prior to joining is higher than the surfaceroughness in the structure of FIG. 2 a.

FIG. 3b is an illustrative light optical photomicrograph at 100×depicting a microstructure expected within the present teachings inwhich no bonding agent (e.g., no powder, foil or other added material)is employed for joining between blocks of a target body, and in whichsurface roughness of blocks prior to joining is higher than the surfaceroughness in the structure of FIG. 2 a.

FIG. 4 is an illustrative scanning electron microscope backscatterphotomicrograph at 500× for illustrating phases typically expected in ahot isostatically pressed target body made from blocks having a mixtureof 50 at % molybdenum and 50 at % titanium powders, as described inExample 1, which are joined together in the absence with no bondingagent (e.g., no powder, foil or other added material).

DETAILED DESCRIPTION

Turning now in more detail to particular teachings of the presentinvention, in general, the present teachings envision a relatively largesputtering target, and particularly a sputtering target consolidatedfrom metal powder. The target generally will include a target body(namely, the consolidated portion of the target, and specifically theportion of the overall target assembly that is subjected to bombardmentfor purposes of material removal and sputter deposition) that may bejoined to a backing plate in any suitable art disclosed manner. Thesputtering target body may be any suitable geometry. It may be generallycircular (so that it would have a diameter as its largest dimension). Itmay be rectangular, and thus have one of its side edges as having itslargest dimension (e.g., the length of the side edge). It may betubular. Though the teachings herein also apply to smaller sputteringtargets, they have particular utility for larger scale targets. By wayof example, larger scale target bodies may be sized such that theyexceed about 0.5 meters, about 1 meter, or even about 2 meters for itslargest dimension. Examples of such target bodies may be generallyrectangular targets having a length that exceeds about 0.5 meters, about1 meter, or even about 2 meters. Such target bodies may have a widththat exceeds about 0.5 meters, about 1 meter, or even about 2 meters.The resulting target bodies may exceed about 0.3 square meters (m²), 0.5m², 1 m², or even 2 m² for the target sputtering surface available forsputtering.

The target body is typically made to include at least two consolidatedpreformed blocks. The consolidated blocks will typically be sized (e.g.,length, width, area, or any combination thereof) to be smaller than theoverall resulting target body. For example, they may be about one half(or smaller) the size (e.g., length, width, or area) of the desiredresulting target body (e.g., they may be about 1/n the size of thedesired resulting target body, wherein n refers to the total number ofconsolidated blocks). Each of the consolidated blocks may each beapproximately the same size as each other block. One or moreconsolidated block may be smaller than another other blocks. The blocksmay be of generally the same shape as each other, or they may differ asto shape. The blocks may have a generally rectangular prism shape. Theblocks may be generally cylindrical. The blocks may include one or morechannels, through holes or other openings. For example, the blocks maybe generally cylindrical and have a through passage for defining atubular shaped block. One or more side walls of the block may begenerally orthogonally oriented relative to a surface that will functionas a sputtering surface. One or more side walls of the block may begenerally oriented at a slope angle of at least ±5°, 10°, 20° or morerelative to a plane that would be perpendicular to a sputtering surface,in this manner it is possible that a joint may employ a scarf jointbetween adjoining blocks. Other joint structures other than a butt jointor a scarf joint may be employed, such as a lap joint, dovetail joint,or any combination of the above joints.

More particularly, a plurality of blocks are prepared by consolidatingpowdered metal. The consolidation may occur from sintering, coldisostatic pressing, hot isostatic pressing, otherwise compacting (e.g.,rolling, die compacting or both) or any combination thereof. Forexample, one approach is to first compact to a predetermined densitythat is less than the theoretical density of the material. This may bedone, for example, by cold isostatically pressing a mass of powders ofthe desired composition (such as is taught in U.S. Patent ApplicationNo. 20070089984 at paragraph 50 through 53, incorporated herein byreference (Gaydos et al)). The resulting compacted forms may be machinedto form block precursor structures. The blocks (or block precursorstructures) may be further densified such as by hot isostaticallypressing. The resulting consolidated blocks are then joined together toform a target body by hot isostatically pressing two of more blocks(e.g., while encapsulated in a suitable hot isostatic pressingcontainer), preferably under conditions so that the resulting blocks arejoined together without any added bonding agent (e.g., in the absence ofany powder, foil or other added material within the space betweenadjoining blocks).

It is contemplated that the starting powdered metals, beforeconsolidation, will include one or more powders of a substantially puremetal (e.g., having a purity (defined to mean free of metallic elements)of at least about 99.5%, 99.95% or even 99.995% purity)).

The powders, before consolidation will typically have an averageparticle size of less than about 50 μm, or even less than about 35 μm,as measured according to ASTM 8822-10. For example molybdenum powders,before consolidation will typically have an average particle size ofless than about 25 μm, or even less than about 5 μm, as measuredaccording to ASTM B822-10. When titanium is employed, the titaniumpowders may have an average particle size of less than about 50 μm, oreven less than about 35 μm. The titanium powders may have an averageparticle size of higher than about 5 μm, or even higher than about 25μm.

Prior to consolidation, powders may be blended in accordance with artdisclosed powder blending techniques. For example, mixing may occur byplacing the molybdenum and titanium powders in a dry container androtating the container about its central axis. Mixing may be continuedfor a period of time sufficient to result in a completely blended anduniformly distributed powder. A ball mill or similar apparatus (e.g.,rotating cylindrical, rotating cone, double cone, twin shell, doubleplanetary, and/or sigma-blade blender) may also be used to accomplishthe blending step.

The composition in each block of the resulting target body willgenerally include molybdenum and at least one additional alloyingelement. For example, the composition may include an alloy includingmolybdenum in an amount so that in the resulting target body there is asubstantially pure phase of molybdenum present in an amount greater thanabout 30 vol %, greater than about 35 vol %, or even greater than about40 vol % of the resulting target block, body or both. The compositionmay include an alloy including molybdenum in an amount so that in theresulting target body there is a substantially pure phase of molybdenumpresent in an amount less than about 50 percent by weight or volume,less than about 48 percent by weight or volume, or even less than about45 percent by weight or volume (e.g., about 43 percent by weight orvolume) of the overall block, body or both. The amount of the molybdenumin the target, the alloy, or both, may range from about 5 to about 95 at%, more preferably about 20 to about 80 at %, still more preferablyabout 30 to about 70 at %. It may be about 40 to about 60 at % (e.g.,about 50 at %). The remaining alloying elements may make up the balance.For example, the amount of titanium in a system employing onlymolybdenum and the additional alloying element powder may be about 100at % minus the amount (in at %) of molybdenum. Thus, as can be seen fromthe above, the teachings contemplate a composition of the target, thealloy, or both, of about 30 to about 70 at % Mo (e.g., about 35 to about65 at % Mo, or even about 40 to about 60 at % Mo) and the balance beingthe at least one additional alloying element, such as titanium (e.g.,about 50 at % Mo and about 50 at % of another element (such astitanium)).

The at least one additional alloying element may be a metallic element,such as one selected from titanium, chromium, niobium, zirconium,tantalum, tungsten or any combination thereof. It is possible that thatat least one additional alloying element may include hafnium and/orvanadium. It is also possible that the at least one additional alloyingelement may include one or more alkali metal (e.g., lithium, sodiumand/or potassium in an amount of less than about 10 at % or even 5 at %of the total composition). Examples of suitable alloying ingredients aredisclosed in PCT Application No. WO2009/134771, and U.S. applicationSer. Nos. 12/990,084; 12/827,550 and 12/827,562 (all incorporated byreference). The amount of the at least one additional alloyingingredient may be such that it will result in (i) a substantially purephase of that alloying element; and/or (ii) an alloy phase that includesmolybdenum and the at least one alloying element. By way of example, theamount of the at least one additional alloying element may be sufficientto obtain a substantially pure phase of the at least one additionalalloying element that is at least about 1, 2, 4 or even about 6 vol % ofthe resulting target body, block or both. The amount of the at least oneadditional alloying element may be sufficient to obtain a substantiallypure phase of the at least one additional alloying element that is lessthan about 30 vol %, 25 vol %, 15 vol % or even about 10 vol % of theresulting target body, block or both.

The amount of each of the molybdenum and the at least one additionalalloying element may be sufficient to realize, in the resulting targetbody, block or both, an alloy phase (i.e., one that includes bothmolybdenum and the at least one additional alloying element) in anamount greater than about 30 vol %, 40 vol %, 44 vol % or even about 48vol %. For example, the alloy may be present as a major constituent ofthe block, by volume. The amount of each of the molybdenum and the atleast one additional alloying element may be sufficient to realize inthe resulting target body an alloy phase that includes both molybdenumand the at least one additional alloying element in an amount less thanabout 70 vol %, 60 vol %, 56 vol % or even about 52 vol %. As can beseen, the alloy phase may be present as a major constituent by volume ofthe block, body or both.

By way of illustration, in the context of a Mo—Ti starting powdermixture material, the resulting target body, both in the original targetblocks and at the joints, is expected to have a vol % pure Mo phase ofabout 30 to about 50% (e.g., about 35 to about 48%, or even about 40 to45%), a vol % pure Ti phase of about 1 to about 25% (e.g., 2 to about15% or even about 5 to 10%) and a vol % of alloy phase of about 30 toabout 70% (e.g., about 40 to about 60% or even about 45 to 55%).

The resulting target bodies of the teachings herein may have some oxygencontent therein. Oxygen may be present in an amount less than about 5000ppm or less than about 4000 ppm. Oxygen may be present in an amountgreater than about 100 ppm, or even about 500 ppm For example, aresulting oxygen weight concentration of the blocks of the sputteringtarget may be between about 1000 ppm and 3500 ppm.

The resulting target body may be further characterized by at least one,preferably a combination of at least two features, more preferably acombination of at least three features, still more preferably acombination of at least four features, and even still more preferably acombination of all features selected from the following features (i)through (v): (i) at least one joint between at least two consolidatedblocks (e.g., side-by-side or end-to-end adjoining blocks) that is freeof an added bonding agent (e.g., powder, foil or otherwise); at leastone joint between at least two consolidated blocks (e.g., side-by-sideor end-to-end adjoining blocks) being essentially free of any ostensibleband or joint line of greater than about 300 μm width (with the widthbeing the average distance between opposing ends of end-to-end adjoinedblocks along the length of the joint) and more preferably free of anyjoint line of greater than about 200 μm width, 100 μm width, or evenabout 50 μm width), where the width is the distance spanning in thedirection between opposing sides of adjoining blocks; (iii) a sputteringtarget body that is at least about 0.5 meters, about 1 meter, or evenabout 2 meters, along its largest dimension, and which exhibits atransverse rupture strength per ASTM B528-10 that is generally uniform(e.g., the fluctuation from low to high is less than about 50% thehighest value, or even less than about 35% of the highest value)throughout the body, including across the joint, and which may be atleast about 400 MPa, 500 MPa, 600 MPa, 700 MPa, 800 MPa or even 900 MPa;(iv) the target body exhibits a Vickers Hardness (HVN) of at least about260, about 275 or even about 300 (e.g., it may have an HVN of about 260to about 325); or (v) the target body may have a density of at leastabout 0.92, about 0.95 or even about 0.98 times the theoretical densityof the overall material (e.g., for a target body that consistsessentially of molybdenum and titanium, the target body may have adensity in the range of about 7.12 to about 7.30, and more specificallyabout 7.20 to about 7.25 g/cm). The sputtering target body may also besufficiently strong so that it withstands, without fracture, routinestresses encountered during subsequent assembly operations (e.g., athree point straightening assembly operation, a creep flatteningoperation, or some other operation during which the target body and anyjoint may be subjected to a load of greater than about 0.6 MPa). Methodsherein thus may include one or more steps of performing an assemblyoperation (e.g., an assembly operation selected from a three pointstraightening operation, a creep flattening operation, or both). Asdiscussed previously, another aspect of the present teachings, which isbelieved to result in sputter target bodies that exhibit one or more ofthe features of the previous paragraph pertains to a methods for makinga sputtering target. Broadly stated, the methods include steps ofconsolidating at least two blocks into performs, and joining the blockstogether. The joining of the blocks is desirably done under heat andpressure, and in a manner that otherwise avoids the need for relianceupon an intermediate bonding agent (e.g., powder, foil or otherwise)between opposing surfaces of the blocks as a primary mode of assuring abond between the blocks. Rather, desirably, the bonding of adjoiningblocks relies mainly upon the formation of at least some metallic bonds(with some mechanical bonding being possible as well) between metal fromopposing surfaces of the blocks.

Accordingly, one approach involves a step of making a plurality ofconsolidated blocks as preforms. The preforms may have substantially thesame composition as each other. The preforms may be made in asubstantially identical manner as each other. The preforms may beconsolidated in any suitable manner. The blocks of the preforms may beany suitable geometry. For example, they may be generally rectangularprisms. They may be generally cylindrical. They may be hollow (e.g.,tubular). Other shapes are also possible.

Typically the manufacture of the blocks will employ a powder startingmaterial. The powder may be densified by the application for a desiredperiod of time of heat, pressure or both. For example, they may becompacted, sintered, cold isostatically pressed, hot isostaticallypressed or any combination thereof. An initial compaction step mayoccur. For example, an initial step may be employed to compact a mass ofpowder to about 50 to about 85% of theoretical density (e.g., about 60to about 70% of theoretical density). This may be done by a suitablecold isostatic pressing operation. One or more secondary operations mayalso be performed, such as a cold working step, a hot working step, anannealing step, or otherwise.

A preferred approach to consolidation includes a step of hotisostatically pressing (HIP) a mass (e.g., an uncompacted powder mass ora compacted powder mass) at a pressure of at least about 100 MPa. TheHIP process desirably may be performed at a temperature below about1080° C. (e.g., at about 1050° C.), 1000° C., 950° C., 900° C., or evenbelow about 850° C. (e.g., at about 825° C.). The HIP process may rangein duration from about 1 to about 12 hours, and more preferably about 4or 6 to about 10 hours (e.g., about 8 hours). By way of example, withoutlimitation, the mass may be pressed to generally rectangular blockshaving a thickness of about 10 mm to about 60 mm, and more preferablyabout 15 mm to about 45 mm (e.g., about 15 mm, about 25 mm, about 35 mmor even about 45 mm). The mass may be pressed into a generallyrectangular block having a width of about 25 to about 100 mm (e.g.,about 30 mm, about 50 mm or even about 90 mm), and more preferably fromabout 30 mm to about 50 mm. The mass may be pressed into a generallyrectangular block having a length of about 70 mm to about 160 mm, andmore preferably about 90 mm to about 150 mm (e.g., about 90 mm, about120 mm, or even about 150 mm).

Two, three, or more blocks are joined to form a target body. Asmentioned, preferably this is done in without employing a bonding agent(e.g., a powder, a foil or any other added material) as the primarymeans of joining. For example, though some amounts of a bonding agentmay be employed, aspects of the present teachings contemplate that thejoining, to make the target body, may be achieved in the absence of anybonding agent. By way of illustration, two blocks may be prepared, eachhaving dimensions of about 1.5 meters long by about 0.9 meters wide byabout 0.16 meters thick. They may be joined together along opposingwidth edges to form a target body. In another illustration, two blocksmay be prepared, each having dimensions of about 1.2 meters long byabout 0.5 meters wide by about 0.46 meters thick. They may be joinedtogether directly along opposing length edges to form a target body. Instill another illustration, two blocks may be prepared, each havingdimensions of about 1.2 meters long by about 0.5 meters wide by about0.3 meters thick. They may be joined together, in end-to-end directcontact with each other (absent any intermediate materials), alongopposing length edges to form a target body. In still yet anotherillustration, three blocks may be prepared, each having dimensions ofabout 0.9 meters long by about 0.3 meters wide by about 0.25 metersthick. They may be joined together end-to-end along opposing lengthedges to form a target body. More than three blocks can be employed,such as an array of two or more blocks along two or more axes.

Following the pressing, but prior to the joining of the perform blocksto form a sputter target body, one or more surfaces of the performblocks may be surface prepared (e.g., surface roughened and/or polished,whether chemically, mechanically, electrochemically, a combinationthereof or otherwise) to impart a desired surface finish, such as forincreasing surface area of the surface for contacting an adjoining blockas compared with a surface that is not surface prepared, or forotherwise increasing contact area between two or more adjoining blocks.For example, surfaces that are to oppose each other when joineddesirably are prepared (e.g., roughened). They may be prepared so as toachieve an arithmetic average surface roughness R_(A) (as measured byASTM 8948-06) that may be at least about 50 μ-in (1.3 μm), or even atleast about 100 μ-in (2.6 μm) (e.g., about 120 μ-in (3 μm) to about 150μ-in (3.8 μm)). They may be prepared so as to achieve an arithmeticaverage surface roughness R_(A) (as measured by ASTM 8946-06) that maybe less than about 200 μ-in (5.1 μm), less than at least about 180 μ-in(4.6 μm), or even less than about 150 μ-in (3.8 μm), or even less thanabout 120 μ-in (3 μm). For example, the arithmetic average surfaceroughness R_(A) (as measured by ASTM B946-06) may range from about 50μ-in (1.3 μm) to about 150 μ-in (3.8 μm)), and more specifically about63 μ-in (1.6 μm) to about 125 μ-in (about 3.2 μm).

After any surface preparation (e.g., surface roughening), at least oneprepared surface of a first block is contacted (e.g., directly and inthe absence of any intermediate bonding agent such as powder, foil orother material) with at least one prepared surface of a second block toform a contacted joint structure. The blocks may be contacted end-to-endalong their respective side edges (e.g., at least partially along alength or a width of each block). It also may be possible to stack twoor more blocks, e.g., in face-to-face opposing relationship. Thecontacted blocks desirably are encapsulated in a pressing vessel, suchas a suitable hot isostatic pressing container (e.g., a mild steel canthat is hermetically sealed for pressing). They are then hotisostatically pressed to a desired shape at a temperature that is lessthan 1100° C. (e.g., about 1080° C., or about 1000° C. or less) and at apressure and for a time sufficient to realize a consolidated jointbetween the first and second blocks. A preferred approach may include astep of hot isostatically pressing a powder mass at a pressure of atleast about 75 MPa, or even at least about 100 MPa. A preferred approachmay include a step of hot isostatically pressing a powder mass at apressure of less than about 300 MPa, less than about 250 MPa, or evenless than about 175 MPa. The HIP process desirably may be performed andat a temperature below about 1080° C. (e.g., about 1050° C.), belowabout 1000° C., below about 950° C., or even below about 900° C. (e.g.,at about 890° C.). As such, the HIP process may be free of a step ofheating the powder, the can, or both to a temperature of about 1100° C.or higher. As seen, it is also possible that the HIP process may be freeof a step of heating the powder, the can, or both to a temperature ofabout 1000° C. or higher. The HIP process may range in duration fromabout 1 to about 16 hours, and more preferably about 3 to about 8 hours(e.g., about 4 hours). After the pressing is completed, the can may beremoved. Other details about pressing operations can be gleaned fromU.S. Pat. No. 7,837,929 ((Gaydos et al) incorporated by reference) (seee.g., the Examples).

As seen from the above, resulting target bodies are of powdered metalorigin and are typically subjected to at least two separate hotisostatic pressing operations at temperatures in excess of about 800°C., at a pressure greater than about 75 Mpa, and for a period of atleast one hour. Unlike in methods that employ a loose powder in theprocessing for bonding joints there is no joint component (e.g., theloose powder, foil or other added material) that is subjected to only asingle hot isostatic pressing operation, and also will be subject to adifferent axial pressure conditions as compared with the adjoiningblocks. Additionally, in contrast with methods that employ a loosepowder between blocks for joining the blocks, it is possible to avoidformation of a band of material (e.g., visible to the naked eye) betweenadjoining blocks that may have a different morphology, average grainsize, phase content or any combination, as compared with the adjoiningblocks.

In yet another aspect of the teachings herein, it is contemplated thatsputtering is performed using a sputtering target in accordance with thepresent teachings. It also is contemplated that thin films result thatare used in any of a number of electronic devices (e.g., as a barrierlayer, and electrode layer or both), such as one or more of television,a video display, a smartphone, a tablet computer, a personal digitalassistant, a navigation device, a sensor, a photovoltaic device, or aportable entertainment device (e.g., video players, music players,etc.).

The thin films may have a reduced amount of structural artifactsattributable to particles as compared with sputtering using targets withpowder joints, and are substantially uniform in structure (e.g., greaterthan about 98%). The thin films may have a thickness of less than about350 nm, less than about 225 nm, or even less than about 100 nm. The thinfilms may have a thickness of greater than about 5 nm, or even greaterthan about 10 nm. For example, the films may have a thickness of about15 to about 25 nm. The thin films may exhibit a resistivity value ofabout 70 to about 90, or even about 75 to about 85 μΩ·cm (using a fourpoint probe). The thin films may exhibit a 5B adhesion rating foradhesion to a substrate made of either Corning 1737 glass or amorphoussilicon (e.g., amorphous silicon coated glass per ASTM D:3369-02). Thethin films preferably exhibit good interfacing capability with copper orother metal conductors, such as copper conductive layers in displaydevices.

The targets herein may be made in a process that is free of any hotworking step, any forging step, or both. Though the temperatures for hotisostatic pressing preferably are below 1100° C., they may be about1100° C. or higher, or even 1200° C. or higher. Though the jointpreferably is free of any bonding agent, it is possible that smallquantities of bonding agent (e.g., a powder, a foil or both may beemployed). For example, it is possible that the teachings herein mayinclude a step of diffusion bonding two or more adjoining blocks with arelatively small quantity of a powder (e.g., for a system that includesMo and at least one other element, Mo powder alone, the other elementpowder alone, or a mixture of powders of Mo and such other elements). Insuch instance, the amount of powder may be an amount that will result ina conspicuous joint line (which may be of sufficient width to appearvisually as a band) from the powder interface that is less than about200 μm in width, less than about 100 μm in width or even less than about50 μm in width.

The teachings herein contemplate that resulting target body materialsinclude at least one pure metallic elemental phase, such as pure Mo (andmore preferably at least two pure metallic elemental phases, such aspure Mo and pure Ti), along with at least one alloy phase (e.g., β(Ti,Mo) phase). However, it is possible that the resulting target body willhave substantially no alloy phase, such as a β(Ti, Mo) phase (i.e.,about 15% (by volume) or less of the β-phase).

The microstructure of resulting target bodies preferably issubstantially uniform throughout the body. In a typical target body thatincludes molybdenum and at least one other element (e.g., Ti), themicrostructure preferably exhibits a matrix of pure molybdenum, withregions of the other element distributed substantially uniformlythroughout the matrix. Regions of the other element phase (e.g.,titanium phase) are generally equiaxed. Regions of the other elementphase (e.g., pure titanium phase) may vary in size substantiallyuniformly throughout the body. For example, such regions may achieve alargest region diameter on the order of about 200 μm. Regions of thepure element phase (e.g., pure titanium phase) may have an averageregion diameter of about 50 to about 100 μm.

Bonding of adjoining blocks may be end-to-end, and thus may take placealong a side edge of a block. It may be face-to-face, and thus may beacross a face of a block (e.g., an upper major surface of one blockopposing a lower major surface of another block), or both.

As to all of the teachings herein, including those in the followingexamples, the volume percent of the respective phases are determined bya method that follows the principles from ASTM standards E562 and E1245.Following this method, an SEM backscatter detection (BSE) mode image istaken such that the phases are distinguishable by the intensity ofpixels in a black-and-white image. Using BSE mode, the number ofscattered electrons will be directly related to atomic number, soheavier elements will appear brighter. For example, the large differencein atomic number of Mo (42) and Ti (22) makes the identification of eachelement possible from a backscatter image. The alloy phase willtypically appear gray, with an intensity between brightest pureelemental (e.g., Mo) regions (showing as the most white) and the darkestpure elemental (e.g. Ti) regions, as illustrated in FIG. 4 below. Byanalyzing a pixel intensity histogram (8-bit image: intensities from0-255), thresholds can be defined and the area percentage of each phasecan be calculated by a pixel count of the intensity range for eachphase. Since the material is believed to be substantially homogeneouswith no preferred direction for any phase, the area percentage istreated as being equal to the volume percentage of each phase. For theabove analysis, the person skilled in the art will recognize that it ispossible that the thresholds may be defined in an objective manner bymeasuring the minima between peaks in a pixel intensity histogramderived from the BSE image. For example, these minima can be calculatedby fitting a 2nd-order polynomial equation to the histogram data at theregions between peaks. The skilled artisan will readily understand that,due to potential minor fluctuations across a sample, an average may betaken of multiple measurements (e.g., measurements may be taken at fivelocations across a sample). Thus, except as stated herein otherwise(e.g., with reference to FIG. 4 below, where a single measurement isillustrated), the expression of results of measurements of the phaseconcentrations herein contemplate an average concentration across asample.

By way of illustration, with reference to FIG. 4, there is showngenerally an illustrative microstructure that may be expected for aMo—Ti target body prepared by hot isostatic pressing of a metal powdermixture having about 50 at % Mo and 50 at % Ti, in accordance with theteachings generally herein (and particularly following the teachings ofExample 1). In these scanning electron microscope images (in backscatterelectron detection mode), the pure titanium phase is the darkest phase.The medium shaded phase essentially surrounding the titanium is atitanium/molybdenum alloy phase (e.g., believed to be a β-phase, butwhich has varying concentrations of titanium and molybdenum throughout),and the lightest phase is molybdenum. For the structure depicted in FIG.4, there is seen to be a volume percentage of β-phase of about 52.9 vol.%, about 40.9 vol % Mo and about 6.1 vol % Ti. The sample itself mayhave a slightly higher or slightly lower overall phase concentrationupon taking multiple measurements at different locations across thesample.

With further reference to the accompanying illustrative figures, in thefollowing examples, there is illustrated a relative comparison ofstructures expected to be realized by practicing the teachings of priorart (i.e., FIGS. 1a and 1b ), in which a powder bonding agent isemployed in a joint between adjoining blocks. In contrast, the FIGS. 2a,2b . 3 a, 3 b, and 4 illustrate structures expected to be realized bypractice consistent with the present teachings, in which a powderbonding agent is omitted in a joint between adjoining blocks.

As the person skilled in the art will appreciate from the abovediscussion and the description that follows, the present teachingscontemplate one or more of the following characteristics and/orvariations. The methods herein may include or may be free of any step ofpulverizing a previously compacted powder (e.g., it is free of any stepof pulverizing a green compact). Prior to any final consolidation step,the methods may include or may be free of any step of employing asecondary powder phase, such as that addressed in Published UnitedStates Patent Application No. 20050230244. The methods herein mayinclude or may be free of any step of forming a cast metal ingot preformblock that is thereafter processed for forming a joined target. Themethods herein may include or may be free of any step of welding (e.g.,friction stir welding) of two or more preform blocks. The methods hereinmay include or may be free of any step of thermo-mechanical working(e.g., rolling) of a preform block, a consolidated target or both. Themethods herein may include or may be free of any step of annealing orother heat treating.

Prior Art Example

For this example, preform blocks are made by hot isostatically pressingan amount of 50 at % molybdenum powder and 50 at % titanium powder at atemperature of about 825° C., for a time of about 8 hours and at apressure of about 175 MPa. The blocks are then placed in a hot isostaticpress container with a powder mixture of about 50 at % Mo and 50 at % Tibetween them. The powder includes titanium powder (Grade Ti-050, havingan average particle size of about 45 to about 150 μm, from ReadingAlloys) and molybdenum powder (MMP-7, having an average particle sizeless than about 70 μm, from H. C. Starck). The powder is handled toavoid molybdenum powder agglomeration. The blocks (with powder betweenthem) are then hot isostatically pressed at a temperature of about 890°C., for a time of about 4 hours and at a pressure of about 100 MPa.Sections are taken of the resulting target body material and examinedmicroscopically by optical microscope. They are also examined by thenaked eye, which reveals a conspicuous band line at the joint. Forillustration purposes, the joint line width for the example hereaverages about 300 μm. Typical commercial scale products, however, willemploy a joint line on the order of about 1 to about 1.5 mm wide. FIG.1a is an illustrative photomicrograph at 25× magnification of a sectionof the target body. FIG. 1b is an illustrative photomicrograph at 100×magnification of a section of the target body. In each of sections shownin FIGS. 1a and 1b a visible band of material can be seen as a jointline in the region where the powder is placed before the second hotisostatic pressing operation. Such band is shown as having a width onthe order of about 300 μm. Other differences in microstructure may alsoexist in such samples, such as a lower concentration of alloy phase inthe joint than in the regions within the original blocks. The morphologyof the pure titanium phase, the pure molybdenum phase or both may alsodiffer from the morphology of such phases in the original blocks,believed to be caused potentially by a greater degree of unlaxialcompression to which the joint is subjected during pressing. Asmentioned previously, the presence of one or any combination of theabove differences between the material in the regions of the joint andthe original blocks is believed by some to be a potential source offormation of particles that may be emitted during sputtering, inasmuchas such differences potentially may affect the uniformity of electricalfield over the target during sputtering.

The sample is expected throughout to have a vol % pure Mo phase of about40 to 45%, a vol % pure Ti phase of about 5 to 10% and a vol % of alloyphase of about 45 to 55%, within the original blocks, and may have aslightly lower concentration of the alloy phase (and higher amounts ofthe pure Mo and Ti) at the joint. The different concentration of phaseswithin the target body is believed due, at least in part, to thedifferent thermal history to which powdered starting materials aresubjected. For example, the powder of the blocks undergoes two hightemperature operations, while the powder of the joint only undergoesone. Accordingly, as can be appreciated, the volume and/or the sizes ofthe individual regions of pure titanium and molybdenum phases may differalso as between the material in the joint and in the regions from theoriginal blocks. It is expected that the transverse rupture strength atthe joint will be about 690 to about 760 MPa.

Example 1

For this example, perform blocks are made by hot isostatically pressingan approximate amount of 50 at % molybdenum powder (average particlesize of less than about 70 μm, as described above) and 50 at % titaniumpowder (average particle size of about 45 to about 150 μm, as describedabove) at a temperature of about 825° C., for a time of about 8 hoursand at a pressure of about 175 MPa. Blocks are water jet cut into a puckshape with an outer diameter of about 10 cm. Edges of the puck shapedblocks are surface machined (e.g., by a first rough milling step,followed by a second milling step) to a surface roughness value (perASTM B946-06) or R_(A) between 120 and 150 μin (3.2 to 3.8 μm). Theblocks are then placed in a hot isostatic press container with preparededges adjoining each other, in the absence of any powder mixture betweenthem. The blocks (with no powder between them) are then hotisostatically pressed at a temperature of about 890° C., for a time ofabout 4 hours and at a pressure of about 100 MPa. Sections are taken ofthe resulting target body material and examined microscopically byoptical microscope. They are also examined by the naked eye, duringwhich a joint line is seen as only faintly visible. Such joint linewidth is substantially smaller than 50 μm, and no band of anyappreciable width is visible.

Similar microstructural results and properties are believed possible forthis Example and Example 2 by using blocks that are pre-formed by beinghot isostatically pressed at about 750° C., for a time of about 4 hoursand at a pressure of about 175 MPa, and then heat treated at atemperature of about 750° C. for about 5 hours.

FIG. 2a is an illustrative photomicrograph at 25× depicting amicrostructure expected within the present teachings in which no bondingagent is employed between blocks of a target body. FIG. 2b is anillustrative photomicrograph at 100× depicting a microstructure expectedwithin the present teachings in which no bonding agent is employedbetween blocks of a target body, in these micrographs the titanium isshown as the lighter grey bodies. The molybdenum is shown also as greybodies, but appears generally as a continuous network surrounding the Tiparticles. Regions of the pure titanium phase appear to be substantiallyuniformly distributed throughout the body. Regions of the pure titaniumphase are generally equiaxed. The uniform distribution and equiaxedshape of the titanium regions across the entire target body that isattainable by the teachings herein is believed to contribute toconsistent and uniform sputtering behavior across the entire target bodyand is also believed to contribute to the absence of undesired particleformation.

As also apparent, regions of the pure titanium may vary in sizesubstantially uniformly throughout the body, and may achieve a largestregion diameter on the order of about 200 μm. Regions of the puretitanium have an average region diameter of about 50 to about 100 μm.

As illustrated, surrounding one or more (or even substantially all)titanium regions may be an alloy of molybdenum and titanium, which maybe of varying composition. The volume of the alloy phase, and/or thethickness of any surrounding layer of it is typically time and/ortemperature dependent. For instance, as the time and temperature of theprocessing steps is increased, the volume and/or thickness of the alloyphase is expected to grow. Pure molybdenum regions will generallysurround the titanium, and the alloy phase, and will form a generallycontinuous molybdenum network throughout the target body.

As can be seen, a target body is made by joining two blocks where thejoint between the two original blocks is free of any bonding agent. Inthis manner, substantially the entirety of material in the target bodyexperiences the same thermo-mechanical processing and is thereforeexpected to have common microstructural characteristics, such as isdepicted. The joints seen in FIGS. 2a and 2b (which joint is to beexpected for other bodies prepared in accordance with the teachingsherein, as well) can be characterized (when magnified by at least 25×)by a mere faint interruption in the continuity of the microstructure,but without any significant changes across the joint. The microstructureon either side of the joint is essentially indistinguishable from themicrostructure on the other side. There is an absence of coarsening ofgrains at the joint. Grains at the joint desirably are of substantiallyidentical morphology as grains within the central portions of theoriginal blocks. In some cases, the effects of preparing the surface forpowderless bonding can be seen by a smearing of the material at thejoint due to machining with a mill, lathe or grinding tool. It may bepossible to reduce the incidence of the smearing by employing one ormore suitable surface preparation techniques, such as by etching. Thesample is expected to have a transverse rupture strength at the jointper ASTM 8528-10 of at least about 400 MPa (e.g., about 690 MPa ormore), a Hardness of 275-310 by ASTM E384-10, and a density of about7.15-7.30 by ASTM B311-08. As discussed, FIG. 4 corresponds with astructure resulting from sample preparation as may be used to preparesamples of FIGS. 2a and 2b respectively, and depict the microstructuresin backscatter mode. As seen, even without any added powder at thejoint, it is surprisingly possible to still realize good mechanicalproperties, even comparable to powder joints of the prior art. Further,the microstructure does not appear to be compromised by the absence ofthe intermediate powder.

Example 2

For this example, perform blocks are made by hot isostatically pressingan amount of 50 at % molybdenum powder and 50 at % titanium powder at atemperature of about 825° C., for a time of about 8 hours and at apressure of about 175 MPa. Puck-shaped blocks (e.g., generallycylindrical bodies having an outer diameter of about 10 cm) are cut fromthe pressed blocks by a waterjet cutter. Surfaces of the puck-shapedblocks are surface machined (e.g., by milling) to a surface roughnessvalue (per ASTM B946-06) or R_(A) in excess of 150 μmin. The puck-shapedblocks (with no powder between them) are then hot isostatically pressedat a temperature of about 890° C., for a time of about 4 hours and at apressure of about 100 MPa. Sections are taken of the resulting targetbody material and examined microscopically by optical microscope,revealing a substantially uniform microstructure. They are also examinedby the naked eye, which reveals only a faint and barely visible jointline.

FIG. 3a is an illustrative photomicrograph at 25× depicting amicrostructure expected within the present teachings in which no bondingagent is employed between blocks of a target body, and in which surfaceroughness of blocks prior to joining is higher than the surfaceroughness in the structure of FIG. 2 a.

FIG. 3b is an illustrative photomicrograph at 100× depicting amicrostructure expected within the present teachings in which no bondingagent is employed between blocks of a target body, and in which surfaceroughness of blocks prior to joining is higher than the surfaceroughness in the structure of FIG. 2 a.

As can be seen, a target body is made by joining two blocks where thejoint between the two original blocks is free of any bonding agent. Inthis manner, substantially the entirety of material in the target bodyexperiences the same thermo-mechanical processing and is thereforeexpected to have common microstructural characteristics, such as isdepicted. The joints seen in FIGS. 3a and 3b can be characterized (whenmagnified by at least 25×) by a mere faint interruption in thecontinuity of the microstructure, but without any significant changesacross the joint (which joint is to be expected for other bodiesprepared in accordance with the teachings herein, as well). Themicrostructure on either side of the joint is essentiallyindistinguishable from the microstructure on the other side. There is anabsence of coarsening of grains at the joint. Grains at the jointdesirably are of substantially identical morphology as grains within thecentral portions of the original blocks. In some cases, the effects ofpreparing the surface for powderless bonding can be seen by anappearance of slight amounts of “smearing” of the material at the jointdue to machining, such as with a mill, lathe or grinding tool. Thoughsuch smearing is not believed to affect performance, this optionally maybe substantially avoided by further machining, by etching, or by someother suitable surface preparation prior to hot isostatic pressing ofblocks.

The sample is expected to have a transverse rupture strength per ASTMB528-10 of at least about 400 MPa (e.g., about 480 MPa) at the joint, aVickers Hardness per ASTM E384-10 of 275-310 (average of indents persample=5; 10 kg test load) and a density per ASTM B311-08 of about 7.15to about 7.3 g/cm³. The sample is expected throughout to have a vol %pure Mo phase of about 35 to about 48% (or even about 40 to 45%), a vol% pure Ti phase of about 2 to about 15% (or even about 5 to 10%) and avol % of alloy phase of about 40 to about 60% (or even about 45 to 55%).

Examples 3-20

Preform blocks are prepared as described in Example 1 except having thecompositions below in Tables 1-3. The edges of the blocks are machinedto the approximate roughness value (per ASTM B946-06) or R_(A) as statedbelow and the resulting blocks are encapsulated in a hot isostatic presscontainer with prepared edges adjoining each other, in the absence ofany powder mixture or other material between them. They are hotisostatically pressed at the temperature indicated, under the pressureindicated and for the time indicated in the processing conditions. Thelatter two columns demonstrate the expected results. Similar results areexpected for blocks that are pre-formed by being hot isostaticallypressed at about 750° C., for a time of about 4 hours and at a pressureof about 175 MPa, and then heat treated at a temperature of about 750°C. for about 5 hours. The transverse rupture strength below refers tothe strength at the joint, and is measured in accordance with ASTM8528-10.

The sample is expected to have a transverse rupture strength (TRS) perASTM B528-10 of at least about 400 MPa (e.g., about 480 MPa) at thejoint, a Vickers Hardness per ASTM E384-10 of 275-310 (average ofindents per sample=5; 10 kg test load) and a density per ASTM 8311-08 ofabout 7.15 to about 7.3 g/cm3. The sample is expected to have a vol %pure Mo phase of about 35 to about 48% (or even about 40 to 45%), a vol% pure Ti phase of about 2 to about 15% (or even about 5 to 10%) and avol % of alloy phase of about 40 to about 60% (or even about 45 to 55%)

TABLE 1 Visible Joint Sample Line Composition: 40 at % Mo—60 at Width <Ex. % Ti (Processing conditions below) 100 μm TRS > 690 MPa 3 1080° C./3hours/150 MPa/3.8 μm R_(A) Yes Yes 4 890° C./4 hours/100 MPa/3.8 μmR_(A) Yes Yes 5 825° C./6 hours/150 MPa/3.8 μm R_(A) Yes Yes 6 1080°C./3 hours/150 MPa/1.6 μm R_(A) Yes Yes 7 890° C./4 hours/100 MPa/1.6 μmR_(A) Yes Yes 8 825° C./6 hours/150 MPa/1.6 μm R_(A) Yes Yes

TABLE 2 Visible Joint Line Sample Composition: 60 at % Mo—40 at Width <TRS > Ex. % Ti (Processing conditions below) 100 μm 690 MPa 9 1080° C./3hours/150 MPa/3.2 μm R_(A) Yes Yes 10 890° C./4 hours/100 MPa/3.2 μmR_(A) Yes Yes 11 825° C./6 hours/150 MPa/3.2 μm R_(A) Yes Yes 12 1080°C./3 hours/150 MPa/1.6 μm R_(A) Yes Yes 13 890° C./4 hours/100 MPa/1.6μm R_(A) Yes Yes 14 825° C./6 hours/150 MPa/1.6 μm R_(A) Yes Yes

TABLE 3 Visible Joint Line Sample Composition: 50 at % Mo—50 at Width <TRS > Ex. % Ti (Processing conditions below) 100 μm 690 MPa 15 1080°C./3 hours/150 MPa/3.2 μm R_(A) Yes Yes 16 890° C./4 hours/100 MPa/3.2μm R_(A) Yes Yes 17 825° C./6 hours/150 MPa/3.2 μm R_(A) Yes Yes 181080° C./3 hours/150 MPa/1.6 μm R_(A) Yes Yes 19 890° C./4 hours/100MPa/1.6 μm R_(A) Yes Yes 20 825° C./6 hours/150 MPa/1.6 μm R_(A) Yes YesGeneral Remarks

As to all of the foregoing general teachings, as used herein, unlessotherwise stated, the teachings envision that any member of a genus(list) may be excluded from the genus; and/or any member of a Markushgrouping may be excluded from the grouping. Percentages of thesputtering target expressed herein refer to the material of thesputtering target available for sputter deposition, and do not includeother sputter target components, such as backing plates.

The skilled artisan will appreciate that references to being “visible tothe naked eye” is regarded as being from the standpoint of a person withaverage vision (e.g., about 20120 vision), unaided by opticalmagnification.

The skilled artisan will also appreciate that discussion of anymicrostructure herein contemplates that samples are prepared usingconventional metallographic sample preparation techniques for theanalysis described. For example, samples may be a mounted section ofmaterial that is ground, polished and optionally etched to reveal themicrostructure. For analysis of joint lines, the teachings hereinenvision that the joint lines are viewed in a target body that has beensubject only to conventional finishing operations. However, theteachings are also applicable to joint lines viewed in a target body (orsection thereof) that has been subject of conventional metallographicsample preparation techniques. Thus, it is possible for the teachingsherein that the joint line widths expressed are observed followingconventional metallographic sample preparation techniques, in theabsence of any metallographic sample preparation techniques, or both.Further, the joint line widths may be measured unaided by microscopy (ifpossible), with microscopic assistance, or both, and are expected toyield similar results. It will be appreciated that one of the benefitsof the present invention is that it may be possible to achieve jointlines that require magnification to detect and/or measure in a finishedtarget. In contrast, with prior techniques that have employed a powderfor diffusion bonding a joint, the resulting joint line has beensufficiently large that it is visible to the naked eye (e.g., appearingtypically as a band) after conventional finishing operations for thetarget body.

Unless otherwise stated, any numerical values recited herein include allvalues from the lower value to the upper value in increments of one unitprovided that there is a separation of at least 2 units between anylower value and any higher value. As an example, if it is stated thatthe amount of a component, a property, or a value of a process variablesuch as, for example, temperature, pressure, time and the like is, forexample, from 1 to 90, preferably from 20 to 80, more preferably from 30to 70, it is intended that intermediate range values such as (forexample, 15 to 85, 22 to 68, 43 to 51, 30 to 32 etc.) are within theteachings of this specification. Likewise, individual intermediatevalues are also within the present teachings. For values which are lessthan one, one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 asappropriate. These are only examples of what is specifically intendedand all possible combinations of numerical values between the lowestvalue and the highest value enumerated are to be considered to beexpressly stated in this application in a similar manner. As can beseen, the teaching of amounts expressed as “parts by weight” herein alsocontemplates the same ranges expressed in terms of percent by weight.Thus, an expression in the Detailed Description of the invention of arange in terms of at “‘x’ parts by weight of the resulting polymericblend composition” also contemplates a teaching of ranges of samerecited amount of “x” in percent by weight of the resulting polymericblend composition.

Unless otherwise stated, all ranges include both endpoints and allnumbers between the endpoints. The use of “about” or “approximately” inconnection with a range applies to both ends of the range. Thus, “about20 to 30” is intended to cover “about 20 to about 30”, inclusive of atleast the specified endpoints. Concentrations of ingredients identifiedin Tables herein may vary ±10%, or even 20% or more and remain withinthe teachings.

The disclosures of all articles and references, including patentapplications and publications, are incorporated by reference for allpurposes. The term “consisting essentially of” to describe a combinationshall include the elements, ingredients, components or steps identified,and such other elements ingredients, components or steps that do notmaterially affect the basic and novel characteristics of thecombination. The use of the terms “comprising” or “including” todescribe combinations of elements, ingredients, components or stepsherein also contemplates embodiments that consist essentially of, oreven consist of the elements, ingredients, components or steps. Pluralelements, ingredients, components or steps can be provided by a singleintegrated element, ingredient, component or step. Alternatively, asingle integrated element, ingredient, component or step might bedivided into separate plural elements, ingredients, components or steps.The disclosure of “a” or “one” to describe an element, ingredient,component or step is not intended to foreclose additional elements,ingredients, components or steps. All references herein to elements ormetals belonging to a certain Group refer to the Periodic Table of theElements published and copyrighted by CRC Press, Inc., 1989. Anyreference to the Group or Groups shall be to the Group or Groups asreflected in this Periodic Table of the Elements using the IUPAC systemfor numbering groups. It is understood that the above description isintended to be illustrative and not restrictive. Many embodiments aswell as many applications besides the examples provided will be apparentto those of skill in the art upon reading the above description. Thescope of the invention should, therefore, be determined not withreference to the above description, but should instead be determinedwith reference to the appended claims, along with the full scope ofequivalents to which such claims are entitled. The disclosures of allarticles and references, including patent applications and publications,are incorporated by reference for all purposes. The omission in thefollowing claims of any aspect of subject matter that is disclosedherein is not a disclaimer of such subject matter, nor should it beregarded that the inventors did not consider such subject matter to bepart of the disclosed inventive subject matter.

What is claimed is:
 1. A process comprising: sputtering a sputteringtarget to form a film over a substrate, wherein the sputtering targetcomprises: a) at least two consolidated blocks, each block including analloy including molybdenum in an amount greater than about 30 percent byweight and at least one additional alloying element; and b) a jointbetween the at least two consolidated blocks, which joins the blockstogether to define a target body, wherein (i) within the at least twoconsolidated blocks there is (a) a molybdenum phase, (b) a phase of theat least one additional alloying element, and (c) a third phasecomprising an alloy of molybdenum at the at least one additionalalloying element, (ii) the third phase is present in an amount greaterthan 30 volume percent, and (iii) the molybdenum phase is present in anamount greater than 30 volume percent.
 2. The process of claim 1,wherein the joint is free of any microstructure due to an added bondingagent.
 3. A process comprising: sputtering a sputtering target to form afilm over a substrate, wherein the sputtering target comprises: a) atleast two consolidated blocks, each block including an alloy includingmolybdenum in an amount greater than about 30 percent by weight and atleast one additional alloying element; and b) a joint between the atleast two consolidated blocks, which joins the blocks together to definea target body, wherein (i) within the at least two consolidated blocksthere is (a) a molybdenum phase, (b) a phase of the at least oneadditional alloying element, and (c) a third phase comprising an alloyof molybdenum at the at least one additional alloying element, (ii) thethird phase is present in an amount greater than 30 volume percent,(iii) the joint is free of any microstructure due to an added bondingagent, and (iv) the sputtering target at the joint exhibits a transverserupture strength per ASTM B528-10, of at least 800 MPa.
 4. The processof claim 1, wherein the joint is essentially free of any joint line ofgreater than about 300 μm width.
 5. The process of claim 1, wherein thejoint is essentially free of any joint line greater than 200 μm widthand the sputtering target at the joint has a transverse rupture strengthper ASTM B528-10, of at least 900 MPa.
 6. The process of claim 1,wherein the at least one alloying element is selected from titanium,chromium, niobium, tantalum, tungsten, zirconium, hafnium, vanadiumlithium, sodium, potassium or any combination thereof.
 7. The process ofclaim 1, wherein the at least two consolidated blocks include a firstblock and a second block, and the consolidated joint includes a directcontact between a prepared surface of first block with a preparedsurface of the second block.
 8. The process of claim 7, wherein theprepared surfaces are milled edge surfaces having an average surfaceroughness (Ra) of less than about 5.1 μm.
 9. The process of claim 7,wherein the prepared surfaces are milled edge surfaces having an averagesurface roughness (Ra) of less than about 3.8 μm.
 10. The process ofclaim 1, wherein each of the consolidated blocks includes about 30 toabout 70 at % molybdenum and the balance titanium, exclusive ofimpurities.
 11. The process of claim 1, wherein an oxygen weight of thesputtering target is between about 1000 ppm and 3500 ppm.
 12. Theprocess of claim 1, wherein the target has a sputtering surface of atleast about 1.5 m², and the two or more consolidated blocks are joinedend-to-end.
 13. The process of claim 12, wherein the sputtering targetincludes about 30 to about 70 at % molybdenum and the balance titanium,exclusive of impurities.
 14. The process of claim 1, wherein thesubstrate comprises at least one of glass or silicon.
 15. The process ofclaim 1, further comprising forming a metal conductor in contact withthe film.
 16. The process of claim 15, wherein the metal conductorcomprises copper.
 17. The process of claim 1, further comprising formingan electronic device incorporating at least a portion of the film. 18.The process of claim 17, wherein the electronic device comprises atelevision, a video display, a smartphone, a tablet computer, a personaldigital assistant, a navigation device, a sensor, a photovoltaic device,or a portable entertainment device.
 19. A process comprising: sputteringa sputtering target to form a film over a substrate, wherein thesputtering target comprises: a) at least two consolidated blocks, eachblock including an alloy including molybdenum in an amount greater thanabout 30 percent by weight and at least one additional alloying element;and b) a joint between the at least two consolidated blocks, which joinsthe blocks together to define a target body, wherein (i) within the atleast two consolidated blocks there is (a) a molybdenum phase, (b) aphase of the at least one additional alloying element, and (c) a thirdphase comprising an alloy of molybdenum at the at least one additionalalloying element, (ii) the third phase is present in an amount greaterthan 30 volume percent, and (iii) the joint comprises at least one of ascarf joint, a lap joint, or a dovetail joint.
 20. The process of claim2, wherein the sputtering target at the joint exhibits a transverserupture strength per ASTM B528-10, of at least 800 MPa.
 21. The processof claim 1, wherein the joint comprises at least one of a scarf joint, alap joint, or a dovetail joint.
 22. The process of claim 19, wherein thejoint comprises a scarf joint.
 23. The process of claim 19, wherein thejoint comprises a lap joint.
 24. The process of claim 19, wherein thejoint comprises a dovetail joint.